CN109722308A - A method of producing low-sulfur, low-alkene gasoline - Google Patents
A method of producing low-sulfur, low-alkene gasoline Download PDFInfo
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Abstract
A method of producing low-sulfur, low-alkene gasoline, it is cut after adding hydrogen including full distillation gasoline raw material, obtain light fraction gasoline and heavy distillat gasoline, light fraction gasoline carries out etherification process and obtains etherificate light fraction gasoline, heavy distillat gasoline carries out hydrodesulfurization and isomerization reaction obtains plus hydrogen heavy distillat gasoline, gained is etherified light fraction gasoline and mixes with hydrogen heavy distillat gasoline is added, and obtains the gasoline products of low-sulfur, low alkene.The present invention can handle the catalytically cracked gasoline of the high alkene of high-sulfur, and product sulfur content and olefin(e) centent meet the gasoline of six gasoline standard of state.Processing method does not have alkali cleaning subtractive process, more environmentally-friendly, and octane number do not lose or lose it is small.
Description
Technical field
The present invention provides a kind of method for producing low-sulfur, low-alkene gasoline.
Background technique
As China's car ownership increases sharply, motor vehicle exhaust emission causes atmosphere polluting problem to get worse.Automobile
The pollutant of exhaust emissions mainly includes SOx and NOx.This pollutant not only results in acid rain, can also destroy ozone layer, and
NOx can also make human carcinogen, cause very big harm to the mankind and environment.Sulphur in gasoline can be such that purifying vehicle exhaust is catalyzed
Agent poisoning, seriously affects it to the processing capacity to discharge pollutants.Therefore, the gasoline being increasingly stringenter has been formulated in countries in the world
Quality standard limits the sulfur content in gasoline.The areas such as Beijing take the lead in implementing and the comparable capital V quality standard of the Europe V (μ of S < 10 g/
g).Sulfur content in gasoline is not only required in following state's VI gasoline standard, it is also possible to it is required that olefin(e) centent is not more than 15%.Commodity
Gasoline is reconciled by basic materials such as straight-run naphtha, reformate, catalytically cracked gasoline, gasoline alkylates.It is domestic at present
In merchantable gasoline blend component, catalytically cracked gasoline is main source, account for about gasoline pool total amount 70~80% (foreign countries account for about 30
~40%), sulfur content of catalytic cracking gasoline is higher, and 90% or more sulphur is from catalytically cracked gasoline in gasoline products.And
Catalytic gasoline olefin(e) centent is also high, and usually about 20%~60%.As it can be seen that reducing sulfur content of catalytic cracking gasoline and olefin(e) centent
It is the key that production clean gasoline.
CN1958740A reports the method for hydrotreating of a kind of deep desulfurization of gasoline, Olefin decrease.Gasoline stocks first add first
Selective hydrodesulfurization reaction, the effluent of reaction effluent and the second hydrotreating reactor are carried out in hydrogen treatment reactor
Mixing, is segmented into different fractions after refrigerated separation in fractionating column inscribe.Light gasoline fraction enters products pot；Optional middle gasoline
Fraction returns to the first hydrotreating reactor, and remaining middle gasoline fraction enters products pot；Heavy naphtha it is all or part of into
Enter the second hydrotreating reactor, carry out hydrodesulfurization and octane value recovering reaction, remaining heavy naphtha enters products pot.
Gasoline products are finally obtained by products pot.The present invention can handle the catalytically cracked gasoline of the high alkene of high-sulfur, and desulfurization degree is up to 90
Weight % or more, yield of gasoline are up to 95 weight % or more, although olefin(e) centent declines about 15 percentage points, loss of octane number is small.
CN101270301A reports a kind of Etherification of Light FCC Gasoline technique and the modifying catalytically cracked gasoline method containing the technique,
Be by the alkadienes and mercaptan sulfur in the chosen property hydrogenation and removing gasoline of FCC gasoline, add after hydrogen by full distillation gasoline be cut into it is light,
Two components are weighed, a large amount of Tertiary olefin has been concentrated in light petrol, warp and methanol are etherified under the action of catalyst for etherification through two sections
At ether compound, the hydrogenated desulfurating and reducing olefinic hydrocarbon of heavy petrol, the heavy vapour in removing sulfide and after reducing olefin(e) centent, after adding hydrogen
Aromatic hydrocarbons in oil is more, can be extracted aromatic hydrocarbons, the heavy petrol after extracting aromatic hydrocarbons is rich in the gasoline component of alkane, can make steam heat
The raw material of cracking ethylene preparation, can also reconcile with etherified benzine is clean gasoline product.
A kind of method that CN102041086A reports high-sulfur, high Olefinic catalytic cracking gasoline cleaning metaplasia produces, it be by
Catalytic gasoline of whole fraction enters selective hydrogenation, carries out adding hydrogen using gasoline hydrogenation pretreatment catalyst, by adding hydrogen de-
Small molecule mercaptan, thioether, disulfide isoreactivity sulfide out, process for selective hydrogenation condition are as follows: hydrogen partial pressure be 1.5~
3.0MPa, reaction temperature are 200 DEG C~260 DEG C, and volume space velocity is 6.0h when liquid-1~12.5h-1, hydrogen to oil volume ratio 150: 1
~500: 1；Selective hydrogenation gasoline is divided into light, heavy naphtha again, then mixes heavy distillat gasoline with hydrogen
After conjunction, into deep hydrodesulfurizationof unit, low-sulfur content heavy fractioning hydrogenation gasoline is obtained using gasoline hydrogenation treatment catalyst,
Hydrofining technology condition are as follows: hydrogen partial pressure is 1.5MPa~2.5MPa, and reaction temperature is 220 DEG C~350 DEG C, volume space velocity when liquid
For 3.0h-1~6.0h-1, hydrogen to oil volume ratio 200: 1~500: 1；Finally light fraction gasoline and heavy fractioning hydrogenation gasoline are reconciled
After obtain IV clean gasoline of state.
A kind of method that CN102851069A reports gasoline desulfurization.The method be gasoline is cut into it is light, weigh two
Fractionation point, light fraction is handled by the way of caustic extraction, and heavy distillat is handled by the way of selective hydrogenation.
A kind of method that CN104277875B reports Deep Desulfurization of FCC Gasoline Olefin decrease is original with catalytic gasoline
Material, first passes through fractionating column and carries out cutting fractionation, be fractionated as light petrol and heavy petrol.It is non-that light petrol enters fixed bed reactors progress
Face hydrogen physical absorption desulfurization, physical absorption desulfurization does not reduce olefin(e) centent, guarantees that the octane number of light petrol does not lose；Heavy petrol with
Hydrogen mixing, into selective hydrodesulfurization fixed bed reactors, reaction product enters back into hydro-upgrading fixed bed reactors, changes
Heavy petrol after matter is mixed with light petrol non-hydrogen physical absorption desulfurization product.Selective hydrodesulfurization is carried out to heavy petrol and is added
Hydrogen modification, because heavy petrol olefin(e) centent is few, and the octane number of this some olefin is low, under conditions of keeping compared with high desulfurization rate,
Heavy petrol loss of octane number is few.The present invention can produce the clean gasoline for meeting Europe IV, taking into account V sulphur index request of Europe, equipment investment
It saves, absorbent filling is convenient, and loss of octane number is few.
In above-mentioned disclosed sulfur method or technique, the problem of being primarily present the following aspects: 1, Olefin decrease energy
Power is insufficient, is unable to reach state VI gasoline standard requirement, because Olefin decrease necessarily brings corresponding RON to lose, must there is phase
The measure answered guarantees the recovery of RON, and the patent use Etherification of Light FCC Gasoline or heavy petrol to modify merely not to be able to satisfy RON extensive
Multiple demand.2, light petrol handles problem, if using caustic extraction method can product alkaline residue emission problem, and subsequent take ether
The method of change still needs pre-hydrotreating, increases complex process degree.
Summary of the invention
The technical problem to be solved by the present invention is to the vapour of the more clean method production low-sulfur of use, low olefin-content
Oil, while guaranteeing that RON does not lose or loses less, the present invention provides a kind of method for producing low-sulfur, low-alkene gasoline.
Method provided by the invention is to include the following steps:
(1) full distillation gasoline raw material and hydrogen mixing connect into the first hydrogenator with the de- diene catalyst of selectivity
Touching is reacted, and the reaction effluent of the first hydrogenator is directly entered the second hydrogenator without isolation and selectivity adds
Hydrogen hydrodesulfurization catalyst, carries out either shallow selective hydrodesulfurization reaction, and the reaction effluent of the second hydrogenator is divided
From obtaining gaseous stream I and liquid phase stream I, resulting liquid phase stream I is fractionated, and light fraction gasoline and heavy distillat are cut into
Gasoline,
(2) the resulting light fraction gasoline of step (1) enters methyltertiarvbutyl ether reactor progress etherification process, obtains etherificate light fraction vapour
Oil,
(3) it after the resulting heavy distillat gasoline of step (1) is mixed with hydrogen, is urged into third hydrogenator and hydrodesulfurization
Agent contact, carries out deep desulfuration, deolefination reaction, and the reaction effluent of third hydrogenator is directly entered the 4th reactor
It is contacted with hydroisomerisation catalysts, carries out isomerization reaction, the 4th reactor reaction effluent obtains after separation plus hydrogen weight
Distillation gasoline,
(4) etherificate light fraction gasoline obtained by step (2) adds hydrogen heavy distillat gasoline to mix with obtained by step (3), obtain low-sulfur,
The gasoline products of low alkene.
The boiling range of full distillation gasoline raw material of the present invention is 30~205 DEG C, the volume fraction of alkene is 5%~
60%, sulfur content is 50~5000 μ g/g.The full distillation gasoline raw material be selected from catalytically cracked gasoline, catalytic cracking gasoline,
Coker gasoline, pressure gasoline, direct steaming gasoline any one of them or several miscellas, preferably catalytically cracked gasoline.
In the present invention, whole-distillate gasoline and hydrogen mixing, into the first hydrogenator, with the de- diene catalyst of selectivity
Contact is reacted, and the alkadienes in full distillation gasoline is mainly removed.By the reaction effluent of the first hydroconversion reaction zone without point
It is contacted from the second hydrogenator is directly entered with catalyst for selectively hydrodesulfurizing, either shallow selection is carried out under conditions of mitigation
Property hydrodesulfurization reaction.The most of non-thiophene-type sulfide of removing.Since non-thiophene-type sulfide compares appearance in full distillation gasoline
Easily removing, in the selective hydrodesulfurization reaction process of the second hydrogenator, it is de- that non-thiophene-type sulfide first carries out reaction
It removes, therefore the reaction condition of the second hydrogenator more mitigates, mainly removes non-thiophene-type sulfide, if hydroconversion condition mistake
In harshness, due to containing a large amount of alkene in light fraction, olefin saturation speed is accelerated, and the RON loss of reaction process will substantially
Increase, therefore the control of its desulfurization degree, 20%~80%, preferred scope is 30%~70%.
Preferably, the reaction condition of first hydroconversion reaction zone are as follows: hydrogen partial pressure 1.0~4.0MPa, more preferable 1.0~
3.0MPa, 80~300 DEG C of reaction temperature, more preferable 120~270 DEG C, 2~10h of volume space velocity-1, more preferable 6~10h-1, hydrogen oil
200~1000Nm of volume ratio3/m3, more preferable 300~800Nm3/m3。
Preferably, the reaction condition of second hydrogenator are as follows: hydrogen partial pressure 1.0~3.0MPa, more preferable 1.2~
2.5MPa, 180~320 DEG C of reaction temperature, more preferable 200~280 DEG C, 1.0~5.0h of volume space velocity-1, more preferable 1.5~
4.0h-1, 200~1000Nm of hydrogen to oil volume ratio3/m3, more preferable 300~800Nm3/m3。
Preferably, it is the be supported in alumina support and/or silica-alumina supports that the selectivity, which takes off diene catalyst,
Group vib metal component and/or group VIII metal component catalyst, wherein vib metals group is selected from molybdenum and/or tungsten, the
Group VIII metal group is selected from cobalt and/or nickel.
Preferably, the catalyst for selectively hydrodesulfurizing be supported on alumina support containing at least one the
The catalyst of group VIII metal component and at least one vib metals component, wherein group VIII metal be selected from cobalt and/or
Nickel, vib metals are selected from molybdenum and/or tungsten, are counted by oxide and on the basis of catalyst, the group VIII metal component
Mass fraction is 0.1~6%, and the mass fraction of vib metals component is 1~25%, and the carrier is a kind of bimodal hole oxygen
Change aluminium, characterized with mercury injection method, 0.9~1.2 ml/g of the Kong Rongwei of the carrier, specific surface area is 50~300 meters2/ gram, directly
Diameter is that the pore volume in the hole 10~30nm accounts for the 55~80% of total pore volume, and diameter is that the pore volume in the hole 300~500nm accounts for total pore volume
10~35%.
After non-thiophene-type sulfide and the removing of part thiophene-type sulfide, full distillation gasoline is cut, is cut into
Light fraction gasoline and heavy distillat gasoline.The light fraction gasoline and heavy distillat gasoline cut point is 45 DEG C~75 DEG C, light fraction
Content of sulfur in gasoline is less than or equal to 10 μ g/g.The cut point can be adjusted by the reaction depth of the second hydrogenator
Section, most of thiophene-type sulfide is concentrated in heavy distillat gasoline.
In step (2), light fraction gasoline and low-carbon alcohols are contacted in methyltertiarvbutyl ether reactor with catalyst for etherification, make light fraction vapour
Alkene in oil is reacted with low-carbon alcohols generates ether compound, it is preferable that and the low-carbon alcohols and the molar ratio of alkene are 1.0~1.2,
Reaction temperature is 20 DEG C~200 DEG C, and reaction pressure is 0.3MPa~2.0MPa, and catalyst for etherification is strong acidic ion exchange tree
Rouge, such as sulfonic acid ion exchange resin, the low-carbon alcohols are methanol.It is rich in alkene in light fraction gasoline, etherificate can be passed through
Mode makes alkene and low-carbon alcohols in light fraction gasoline react the high-octane ether compound of generation, to make light fraction gasoline
Octane number improve, and effectively restore the octane number of full distillation gasoline product.
It is preferred that the progress of etherification reaction, by the way of the sequential catalyst rectifying column after fixed bed reactors, to break
The limitation of thermodynamical equilibrium improves the depth that etherification reaction carries out.Olefin removal rate after etherificate in light fraction gasoline is not less than
35%.Light fraction relatively etherificate fore-octane-number after etherificate improves 1.5~3.5 units.
In step (3), after heavy distillat gasoline is mixed with hydrogen, connect into third hydrogenator and Hydrobon catalyst
Touching carries out deep desulfuration, deolefination reaction, removes most sulphur and alkene.The reaction effluent of third hydrogenator is straight
It taps into and is contacted into the 4th reactor with hydroisomerisation catalysts, carry out isomerization reaction, recovered part octane number, the 4th reaction
Device reaction effluent obtains after separation plus hydrogen heavy distillat gasoline.
Preferably, the reaction condition of the third hydrogenator are as follows: hydrogen partial pressure 1.0~6.0MPa, more preferable 2.0~
5.0MPa, 200~350 DEG C of reaction temperature, more preferable 250~320 DEG C, 1.0~8.0h of volume space velocity-1, more preferable 1.5~6h-1, 200~1000Nm of hydrogen to oil volume ratio3/m3, more preferable 300~800Nm3/m3。
Preferably, the reaction condition of the 4th reactor are as follows: hydrogen partial pressure 1.0~6.0MPa, more preferable 2.0~
5.0MPa, 260~460 DEG C of reaction temperature, more preferable 300~400 DEG C, 0.5~6.0h of volume space velocity-1, more preferable 1.0~
4.0h-1, 200~1000Nm of hydrogen to oil volume ratio3/m3, more preferable 300~800Nm3/m3。
Preferably, the Hydrobon catalyst is to be supported on alumina support to contain at least one group VIII
Metal component and at least one vib metals component and one or more of organic matters in alcohol, organic acid and organic amine
Catalyst, wherein group VIII metal be selected from cobalt and/or nickel, vib metals be selected from molybdenum and/or tungsten, in terms of oxide simultaneously
On the basis of catalyst, the mass fraction of the group VIII metal component is 0.5~9%, the quality of vib metals component
Score is 3~40%, and the molar ratio of the organic matter and group VIII metal component is 0.5~2.5, and the carrier is a kind of double
Peak porous aluminum oxide, is characterized with mercury injection method, 0.9~1.2 ml/g of the Kong Rongwei of the carrier, and specific surface area is 50~300 meters2/
Gram, diameter is that the pore volume in the hole 10~30nm accounts for the 55~80% of total pore volume, and diameter is that the pore volume Zhan in the hole 300~500nm is total
The 10~35% of Kong Rong.
Further preferably, the alkene saturation selectivity of the catalyst for selectively hydrodesulfurizing is lower than hydrodesulfurization catalytic
Agent, when reaching identical desulfurization degree in terms of alkene saturation factor, low 10%~70%；Meanwhile the hydrodesulfurization of Hydrobon catalyst
Activity is higher than the hydrodesulfurization activity of catalyst for selectively hydrodesulfurizing, required reaction temperature when reaching identical desulfurization degree
Degree meter is 10~60 DEG C high.
Preferably, the hydroisomerisation catalysts are to be supported on molecular sieve carrier to contain group VIII metal group
Point and optional vib metals component catalyst, wherein group VIII metal is selected from cobalt and/or nickel, and vib metals are selected from
Molybdenum and/or tungsten, the molecular sieve is in faujasite, Beat molecular sieve, ZSM-5 molecular sieve and SAPO-11 molecular sieve
One or more kinds of mixtures.
Further preferably, the hydroisomerisation catalysts, are counted by oxide and on the basis of catalyst, and described
The mass fraction of group VIII metal component is 0.5~9%, and the mass fraction of vib metals component is 3~40%.
Etherificate light fraction gasoline obtained by step (2) adds hydrogen heavy distillat gasoline to mix with obtained by step (3), obtains low-sulfur, low
The gasoline products of alkene.
The present invention can handle the catalytically cracked gasoline of the high alkene of high-sulfur, obtains sulfur content and olefin(e) centent meets six vapour of state
The gasoline products of oil standard.Method provided by the invention does not have alkali cleaning subtractive process, more environmentally-friendly, and octane number does not lose or damages
It loses small.
Detailed description of the invention
Fig. 1 is the flow diagram of the method provided by the invention for producing low-sulfur, low-alkene gasoline.
Specific embodiment
Method provided by the present invention is further detailed with reference to the accompanying drawing, but does not therefore limit this hair
It is bright.
As shown in Figure 1, the method for production low-sulfur provided by the invention, low-alkene gasoline is described in detail as follows: from pipeline 1
Full distillation gasoline raw material exchanged heat by entering heat exchanger 3 after 2 boosting of pump, the raw material after heat exchange and the hydrogen from pipeline 24
It is mixed into the first hydrogenator 4 and carries out de- two alkene reactions of selective hydrogenation, the first hydrogenator effluent is through heat exchanger
5, after heating furnace 6 heats, into the second hydrogenator 7, either shallow selective hydrodesulfurization reaction is carried out.Second hydrogenator
Effluent enters fractionating column 8, and fractionator overhead material enters tower top liquid separation tank 9 by water cooler, and light petrol and hydrogen are carried out
Separation, the hydrogen isolated are incorporated to compressor outlet pipeline and use as recycle hydrogen.The light fraction gasoline isolated passes through pipeline
10, which enter etherificate unit 11, carries out etherification reaction, and the product after reaction is mixed to get full fraction vapour through pipeline 12 and 26 material of pipeline
Oil product.What 8 bottoms material of fractionating column exported after heat exchanger 13 and the material from pipeline 17 are exchanged heat with compressor 23
Hydrogen is mixed into third hydrogenator 14 and carries out deep desulfuration, deolefination reaction.Third hydrogenator effluent is through adding
Hot stove 15 enters the 4th hydrogenator 16 after heating and carries out isomerization reaction, and the 4th hydrogenator outlet material is through pipeline 17
It successively exchanges heat with heat exchanger 13,5 and 3, enters after air-cooled 18, water cooling 19 is cooling after heat exchange through pipeline and enter high pressure separation
Device 20.After high-pressure separator 20 carries out gas-liquid separation, the hydrogen-rich gas at top enters desulfurizing tower 21 through pipeline and removes in hydrogen
H2It boosts through pipeline 22 into circulating hydrogen compressor 23 after S.From the stream passes via line that 20 bottom of high-pressure separator obtains into
Enter stabilizer 25, the light hydrocarbon gas of tower top is extracted out by pipeline, and tower bottom product is mixed through pipeline 26 with the logistics from pipeline 12
To full distillation gasoline product.
The following examples will be further described method provided by the invention, but therefore not limit this hair
It is bright.
It is catalyst A that selective hydrogenation used in embodiment, which takes off diene catalyst, and trade names are RGO-3, by China
The production of Effect of Catalysis In Petrochemistry agent Chang Ling branch company.
Catalyst for selectively hydrodesulfurizing used in embodiment is catalyst B, and Hydrobon catalyst is catalyst C, different
Structure catalyst is catalyst D.
The carrier of catalyst B is bimodal porous aluminum oxide, and 1.0 mls/g of Kong Rongwei, specific surface area is 130 meters2/ gram, diameter
The 40% of total pore volume is accounted for for the pore volume in the hole 10~30nm, diameter is that the pore volume in the hole 300~500nm accounts for the 30% of total pore volume.
Active metal composition are as follows: molybdenum oxide 13.5 is % heavy, and cobalt oxide 4.0 is % heavy.
The carrier of catalyst C is bimodal porous aluminum oxide, and 1.1 mls/g of Kong Rongwei, specific surface area is 150 meters2/ gram, diameter
The 60% of total pore volume is accounted for for the pore volume in the hole 10~30nm, diameter is that the pore volume in the hole 300~500nm accounts for the 15% of total pore volume,
Active metal composition are as follows: tungsten oxide 19 is % heavy, and cobalt oxide 0.04 is % heavy, and nickel oxide 2.0 is % heavy.
When reaching identical desulfurization degree in terms of alkene saturation factor, the alkene saturation factor of catalyst B lower than catalyst C 15%；And
When reaching identical desulfurization degree in terms of required reaction temperature, the reaction temperature of catalyst C is 30 DEG C lower than catalyst B.
The carrier of catalyst D is ZSM-5, active metal composition are as follows: nickel oxide 5.0 is %. heavy
For the hydrodesulfurization performance for giving full play to catalyst, above-mentioned catalyst is required to carry out before contacting formal raw material pre-
Vulcanizing treatment.In comparative example and embodiment set forth below, the method for pre-sulphuration of each catalyst is identical.
Comparative example 1
Using a kind of catalytically cracked gasoline as feedstock oil E, raw material oil nature is as shown in table 1.Whole-distillate gasoline uses this hair
Process flow is handled in bright attached drawing, and the material after the second hydrogenator, which enters in fractionating column, to be cut, wherein
Light fraction gasoline (boiling range C5~60 DEG C) and heavy distillat gasoline (60 DEG C~195 DEG C of boiling range).Wherein light fraction quality of gasoline ratio
It is 25%, heavy distillat quality of gasoline ratio is 75%.Light fraction gasoline after cutting enters etherificate unit and is etherified, and etherificate is anti-
Answering the molar ratio that condition is methanol and alkene is 1.0, and reaction temperature is 80 DEG C, reaction pressure 1.2MPa, and catalyst for etherification is
Macropore sulfonic acid ion exchange resin.Heavy distillat gasoline enter third hydrogenator and the 4th hydrogenator carry out desulfurization and
Isomerization reaction.Light fraction gasoline is mixed to get full distillation gasoline product with hydrogen heavy distillat gasoline is added after etherificate.Wherein second adds
Hydrogen reactor and third hydrogenator use identical catalyst C.
First hydrogenator, the second hydrogenator, third hydrogenator and the 4th hydrogenator are specifically anti-
Answer condition and full distillation gasoline product property as shown in table 2, as can be seen from Table 2, the sulfur content of gained gasoline products is 8 μ g/
G, olefin(e) centent are that 6.5 volume %, RON losses reach 2.5 units.
Embodiment 1
Using a kind of catalytically cracked gasoline as feedstock oil E, raw material oil nature is as shown in table 1.Whole-distillate gasoline uses this hair
Process flow is handled in bright attached drawing, and the material after the second hydrogenator, which enters in fractionating column, to be cut, wherein
Light fraction gasoline (boiling range C5~60 DEG C) and heavy distillat gasoline (60 DEG C~195 DEG C of boiling range).Wherein light fraction quality of gasoline ratio
It is 25%, heavy distillat quality of gasoline ratio is 75%.Light fraction gasoline after cutting enters etherificate unit and is etherified, and etherificate is anti-
Answering the molar ratio that condition is methanol and alkene is 1.0, and reaction temperature is 80 DEG C, reaction pressure 1.2MPa, and catalyst for etherification is
Macropore sulfonic acid ion exchange resin.Heavy distillat gasoline enter third hydrogenator and the 4th hydrogenator carry out desulfurization and
Isomerization reaction.Light fraction gasoline is mixed to get full distillation gasoline product with hydrogen heavy distillat gasoline is added after etherificate.
First hydrogenator, the second hydrogenator, third hydrogenator and the 4th hydrogenator are specifically anti-
Answer condition and full distillation gasoline product property as shown in table 2, as can be seen from Table 2, the sulfur content of gained gasoline products is 8 μ g/
G, olefin(e) centent are that 6.5 volume %, RON losses are only 0.5 unit.
Embodiment 2
Using a kind of catalytically cracked gasoline as feedstock oil F, raw material oil nature is as shown in table 1.Whole-distillate gasoline uses this hair
Process flow is handled in bright attached drawing, and the material after the second hydrogenator, which enters in fractionating column, to be cut, wherein
Light fraction gasoline (boiling range C5~70 DEG C) and heavy distillat gasoline (70 DEG C~195 DEG C of boiling range).Wherein light fraction quality of gasoline ratio
It is 30%, heavy distillat quality of gasoline ratio is 70%.Light fraction gasoline after cutting enters etherificate unit and is etherified, and etherificate is anti-
Answering the molar ratio that condition is methanol and alkene is 1.1, and reaction temperature is 75 DEG C, reaction pressure 1.2MPa, and catalyst for etherification is
Macropore sulfonic acid ion exchange resin.Heavy distillat gasoline enter third hydrogenator and the 4th hydrogenator carry out desulfurization and
Isomerization reaction.Light fraction gasoline is mixed to get full distillation gasoline product with hydrogen heavy distillat gasoline is added after etherificate.
First hydrogenator, the second hydrogenator, third hydrogenator and the 4th hydrogenator are specifically anti-
Answer condition and full distillation gasoline product property as shown in table 2, as can be seen from Table 2, the sulfur content of gained gasoline products is 6 μ g/
G, olefin(e) centent are 3.5 volume %, and RON does not lose.
Embodiment 3
Using a kind of catalytically cracked gasoline as feedstock oil G, raw material oil nature is as shown in table 1.Whole-distillate gasoline uses this hair
Process flow is handled in bright attached drawing, and the material after the second hydrogenator, which enters in fractionating column, to be cut, wherein
Light fraction gasoline (boiling range C5~85 DEG C) and heavy distillat gasoline (85 DEG C~195 DEG C of boiling range).Wherein light fraction quality of gasoline ratio
It is 40%, heavy distillat quality of gasoline ratio is 60%.Light fraction gasoline after cutting enters etherificate unit and is etherified, and etherificate is anti-
Answering the molar ratio that condition is methanol and alkene is 1.0, and reaction temperature is 80 DEG C, reaction pressure 1.2MPa, and catalyst for etherification is
Macropore sulfonic acid ion exchange resin.Heavy distillat gasoline enter third hydrogenator and the 4th hydrogenator carry out desulfurization and
Isomerization reaction.Light fraction gasoline is mixed to get full distillation gasoline product with hydrogen heavy distillat gasoline is added after etherificate.
First hydrogenator, the second hydrogenator, third hydrogenator and the 4th hydrogenator are specifically anti-
Answer condition and full distillation gasoline product property as shown in table 2, as can be seen from Table 2, the sulfur content of gained gasoline products is 5 μ g/
G, olefin(e) centent are that 3.0 volume %, RON losses are only 0.3 unit.
Table 1
| Material name | E | F | G |
| Density (20 DEG C), g/cm3 | 0.7234 | 0.7321 | 0.7311 |
| Sulphur, μ g/g | 1096 | 631 | 600 |
| Olefin(e) centent, volume % | 39.7 | 28.8 | 26.9 |
| Boiling range (ASTM D-86), DEG C | |||
| Initial boiling point | 26 | 37 | 31 |
| 10% | 40 | 52 | 44 |
| 50% | 85 | 96 | 82 |
| The end point of distillation | 190 | 200 | 200 |
| RON | 94.4 | 90.8 | 90.2 |
| MON | 81.6 | 80.7 | 80.2 |
| Anti-knock index | 88.0 | 85.8 | 85.2 |
Table 2
Whole-distillate gasoline progress either shallow is first added hydrogen then to cut by method provided by the invention, gently evaporating after cutting
Divide gasoline not need to carry out alkali density removal of mercaptans again, does not also need to carry out pre-add hydrogen again, etherificate unit can be directly entered, letter
The process of entire sulfur removal technology is changed, while having eliminated lye exhaust emission, has kept entire sulfur removal technology process more environmentally-friendly and excellent
Change, is able to produce six gasoline of state of low-sulfur, low alkene, and RON loss is small or does not lose.
Claims (12)
1. a kind of method for producing low-sulfur, low-alkene gasoline, includes the following steps:
(1) full distillation gasoline raw material and hydrogen mixing, into the first hydrogenator, contacted with the de- diene catalyst of selectivity into
Row reaction, the reaction effluent of the first hydrogenator is directly entered the second hydrogenator without isolation and selective hydrogenation is de-
Sulfur catalyst contact, carries out either shallow selective hydrodesulfurization reaction, and the reaction effluent of the second hydrogenator is separated, obtained
To gaseous stream I and liquid phase stream I, resulting liquid phase stream I is fractionated, and is cut into light fraction gasoline and heavy distillat gasoline,
(2) the resulting light fraction gasoline of step (1) enters methyltertiarvbutyl ether reactor progress etherification process, obtains etherificate light fraction gasoline,
(3) after the resulting heavy distillat gasoline of step (1) is mixed with hydrogen, into third hydrogenator and Hydrobon catalyst
Contact, carries out deep desulfuration, deolefination reaction, and the reaction effluent of third hydrogenator is directly entered the 4th reactor and adds
The contact of hydrogen isomerization catalyst carries out isomerization reaction, and the 4th reactor reaction effluent obtains after separation plus hydrogen heavy distillat
Gasoline,
(4) etherificate light fraction gasoline obtained by step (2) adds hydrogen heavy distillat gasoline to mix with obtained by step (3), obtains low-sulfur, low alkene
The gasoline products of hydrocarbon.
2. according to the method for claim 1, which is characterized in that the boiling range of the full distillation gasoline raw material is 30~205
DEG C, the volume fraction of alkene is 5%~60%, and sulfur content is 50~5000 μ g/g.
3. according to the method for claim 1, which is characterized in that the reaction condition of the first hydrogenator are as follows: hydrogen partial pressure 1.0
~4.0MPa, 80~300 DEG C of reaction temperature, 2~10h of volume space velocity-1, 200~1000Nm of hydrogen to oil volume ratio3/m3；Second adds hydrogen
The reaction condition of reactor are as follows: 1.0~3.0MPa of hydrogen partial pressure, 180~320 DEG C of reaction temperature, 1.0~5.0h of volume space velocity-1, hydrogen
Oil volume is than 200~1000Nm3/m3。
4. according to the method for claim 1, which is characterized in that it is to be supported on oxidation that the selectivity, which takes off diene catalyst,
Vib metals component and/or group VIII metal component catalyst on alumina supporter and/or silica-alumina supports, wherein group VIB
Metal component is selected from molybdenum and/or tungsten, and group VIII metal component is selected from cobalt and/or nickel.
5. according to the method for claim 1, which is characterized in that the catalyst for selectively hydrodesulfurizing is to be supported on oxygen
Change the catalyst containing at least one group VIII metal component and at least one vib metals component on alumina supporter,
Middle group VIII metal is selected from cobalt and/or nickel, and vib metals are selected from molybdenum and/or tungsten,
It is counted by oxide and on the basis of catalyst, the mass fraction of the group VIII metal component is 0.1~6%, Section VI B
The mass fraction of race's metal component is 1~25%, and the carrier is a kind of bimodal porous aluminum oxide, is characterized with mercury injection method, the load
0.9~1.2 ml/g of the Kong Rongwei of body, specific surface area are 50~300 meters2/ gram, diameter is that the pore volume in the hole 10~30nm accounts for
The 55~80% of total pore volume, diameter are that the pore volume in the hole 300~500nm accounts for the 10~35% of total pore volume.
6. according to the method for claim 1, which is characterized in that the light fraction gasoline and heavy distillat gasoline cut point is
45 DEG C~75 DEG C, light fraction content of sulfur in gasoline is less than or equal to 10 μ g/g.
7. according to claim 1 the method, which is characterized in that in step (2), light fraction gasoline and low-carbon alcohols are in etherification reaction
It is contacted in device with catalyst for etherification, reacts alkene and low-carbon alcohols in light fraction gasoline and generate ether compound, the low-carbon
The molar ratio of alcohol and alkene is 1.0~1.2, and reaction temperature is 20 DEG C~200 DEG C, and reaction pressure is 0.3MPa~2.0MPa, ether
Change catalyst is strong-acid ion exchange resin, and the low-carbon alcohols are methanol.
8. according to the method for claim 1, which is characterized in that the reaction condition of third hydrogenator are as follows: hydrogen partial pressure 1.0
~6.0MPa, 200~350 DEG C of reaction temperature, 1.0~8.0h of volume space velocity-1, 200~1000Nm of hydrogen to oil volume ratio3/m3, the 4th
The reaction condition of reactor are as follows: 1.0~6.0MPa of hydrogen partial pressure, 260~460 DEG C of reaction temperature, 0.5~6.0h of volume space velocity-1, hydrogen
Oil volume is than 200~1000Nm3/m3。
9. according to the method for claim 1, which is characterized in that the Hydrobon catalyst is to be supported on carrying alumina
Contain at least one group VIII metal component and at least one vib metals component and selected from alcohol, organic acid on body
With the catalyst of organic matters one or more of in organic amine, wherein group VIII metal is selected from cobalt and/or nickel, vib metals
Selected from molybdenum and/or tungsten,
It is counted by oxide and on the basis of catalyst, the mass fraction of the group VIII metal component is 0.5~9%, Section VI B
The mass fraction of race's metal component is 3~40%, and the molar ratio of the organic matter and group VIII metal component is 0.5~2.5,
The carrier is a kind of bimodal porous aluminum oxide, is characterized with mercury injection method, 0.9~1.2 ml/g of the Kong Rongwei of the carrier compares table
Area is 50~300 meters2/ gram, diameter is that the pore volume in the hole 10~30nm accounts for the 55~80% of total pore volume, diameter is 300~
The pore volume in the hole 500nm accounts for the 10~35% of total pore volume.
10. according to the method for claim 1, which is characterized in that the alkene of the catalyst for selectively hydrodesulfurizing is saturated
Selectivity is lower than Hydrobon catalyst, when reaching identical desulfurization degree in terms of alkene saturation factor, low 10%~70%；Meanwhile adding
The hydrodesulfurization activity of hydrogen desulphurization catalyst is higher than the hydrodesulfurization activity of catalyst for selectively hydrodesulfurizing, to reach identical
Required reaction temperature meter when desulfurization degree is 10~60 DEG C high.
11. according to the method for claim 1, which is characterized in that the hydroisomerisation catalysts are to be supported on molecule
Sieve on carrier containing group VIII metal component and optional vib metals component catalyst, wherein group VIII metal
Selected from cobalt and/or nickel, vib metals are selected from molybdenum and/or tungsten, the molecular sieve be selected from faujasite, Beat molecular sieve,
The mixture of one or more of ZSM-5 molecular sieve and SAPO-11 molecular sieve.
12. according to the method for claim 11, which is characterized in that the hydroisomerisation catalysts, in terms of oxide
And on the basis of catalyst, the mass fraction of the group VIII metal component is 0.5~9%, the matter of vib metals component
Measuring score is 3~40%.
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